EP1144352A2 - Procede de fabrication d'acroleine par oxydation partielle en phase gazeuse catalytique heterogene du propene - Google Patents

Procede de fabrication d'acroleine par oxydation partielle en phase gazeuse catalytique heterogene du propene

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Publication number
EP1144352A2
EP1144352A2 EP00912429A EP00912429A EP1144352A2 EP 1144352 A2 EP1144352 A2 EP 1144352A2 EP 00912429 A EP00912429 A EP 00912429A EP 00912429 A EP00912429 A EP 00912429A EP 1144352 A2 EP1144352 A2 EP 1144352A2
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EP
European Patent Office
Prior art keywords
propene
reaction
acrolein
gas
molecular oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00912429A
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German (de)
English (en)
Inventor
Peter Zehner
Otto Machhammer
Heiko Arnold
Klaus Joachim MÜLLER-ENGEL
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1144352A2 publication Critical patent/EP1144352A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein

Definitions

  • the present invention relates to a process for the preparation of acrolein by heterogeneously catalyzed gas phase partial oxidation of propene with molecular oxygen over catalysts in the solid state.
  • Acrolein is an important intermediate, for example for the production of glutardialdehyde, methionine, polyacid and acrylic acid.
  • acrolein by heterogeneously catalyzed gas phase oxidation of propene with molecular oxygen over catalysts in the solid state of aggregation (cf. for example DE-A 1 962 431, DE-A 2 943 707, DE-PS 1 205 502, EP-A 257 565, EP-A 253 409, DE-AS 2 251 364, EP-A 117 146, GB-PS 1 450 986 and EP-A 293 224).
  • the catalysts to be used are usually oxide compositions which usually ensure a high selectivity of acrolein formation. As part of the by-product spectrum, acrolein formation is often accompanied by a certain formation of acrylic acid.
  • the catalytically active oxide composition can contain only one other element or more than one other element (multielement oxide compositions). Particularly frequently used as catalytically active oxide compositions are those which comprise more than one metallic, in particular transition metallic, element. In this case one speaks of multimetal oxide masses.
  • the multimetal oxide materials are usually not simple physical mixtures of oxides of the elemental constituents, but rather heterogeneous mixtures of complex poly compounds of these elements.
  • Such multimetal oxide compositions generally contain the elements Mo, Bi and Fe.
  • the heterogeneously catalyzed gas phase oxidation of propene to acrolein takes place at elevated temperature (usually a few hundred ° C., typically 200 to 450 ° C.).
  • the heterogeneously catalyzed gas phase oxidation of propene to acrolein is highly exothermic, it is best carried out in a fluidized bed or in a multi-contact tube fixed-bed reactor, through the space surrounding the contact tubes of which a heat exchange medium is passed.
  • the latter procedure is the preferred one (see, for example, DE-A 4 431 957 and DE-A 4 431 949).
  • the working pressure absolute pressure
  • the target implementation takes place during the dwell time of the reaction gas mixture in the catalyst feed through which it is passed.
  • the oxidation reactors are usually charged with a mixture which contains the reactants molecular oxygen and propylene diluted with a gas which is essentially inert under the conditions of gas-phase catalytic partial oxidation.
  • dilution gases are understood, the constituents of which, under the conditions of the heterogeneously catalyzed gas phase partial oxidation, each constituent per se, remain unchanged at more than 95 mol%, preferably at more than 98 mol%.
  • the inert diluent gas usually combines the largest volume fraction of the three components of the feed gas.
  • One task of the inert diluent gas is to absorb and dissipate the heat released during the partial oxidation.
  • a second task of the inert diluent gas is to reduce the tendency of the reaction mixture to explode.
  • a molecular oxygen and a combustible gas such as propylene containing gas mixture is outside the explosion range under specified boundary conditions (pressure, temperature) if there is a combustion (ignition, ignition, etc.) initiated by a local ignition source (e.g. glowing platinum wire). Explosion) can no longer spread from the ignition source in the gas mixture.
  • EP-A 293 224 recommends using a saturated hydrocarbon gas mixture consisting of carbon dioxide, water vapor and 1 to 5 carbon atoms as the inert diluent gas.
  • EP-A 253 409 teaches that inert diluent gases which have an increased molar specific heat are advantageous.
  • DE-A 19 508 531 teaches that inert diluent gases, which in addition to an increased molar specific heat also have the property of flammability, are particularly suitable inert diluent gases.
  • the State of the art furthermore to choose the ratio of molecular oxygen to propene in the reaction gas starting mixture for the catalytic partial oxidation of the propene> 1 and to add the total amount of molecular oxygen required for the catalytic partial oxidation of the propene to the reaction gas starting mixture in full.
  • inert diluent gases to be used are invariably valuable substances which, for cost reasons, are normally separated from the target product as components of the product gas mixture and are recycled (see, for example, EP-A 253 409 ) can be reused as an inert diluent gas (this also applies to the sole use of nitrogen as an inert diluent gas, since the amount of nitrogen introduced when using air as an oxygen source as an oxygen companion would not be sufficient in its quantity as the sole diluent gas for safe process control ; ie, for safety reasons, an additional nitrogen source (usually circular nitrogen) is always required).
  • the aforementioned circuitry is complex (in the event that the product gas mixture of the partial oxidation of propene to acrolein is used directly for a subsequent partial oxidation of the acrolein contained therein to acrylic acid, the cycle gas is usually separated off only after the acrylic acid stage with recycling to the acrolein stage) .
  • the object of the present invention was therefore to provide a process for the preparation of acrolein by heterogeneously catalyzed gas-phase partial oxidation of propene with molecular oxygen on catalysts in the solid state of aggregation, which either only describes the disadvantages of the processes of the prior art reduced form or no longer at all.
  • a process for the production of acrolein by heterogeneously catalyzed gas phase partial oxidation of propene with molecular oxygen over catalysts in the solid state is found, which is characterized in that a reaction gas starting mixture, the propene and molecular oxygen in a ratio CH 6 : 0 2 > 1 contains, at elevated temperature, first passes through a first reaction zone I equipped with a first catalyst charge I in the solid state of aggregation and thereby oxidizes part of the propene contained in the reaction gas starting mixture to acrolein and then to complete the partial oxidation of the propene to acrolein the product gas mixture I emerging from the reaction zone I at elevated temperature by at least one conducts a further reaction zone having a fixed catalyst charge and thereby increases the molar ratio of molecular oxygen to propene present in the reaction gas mixture in at least one of the further reaction zones by metering in molecular oxygen and / or a gas containing molecular oxygen, with the proviso
  • the advantage of the process according to the invention over the processes of the prior art lies in the fact that the reaction gas mixture in each reaction zone, based on the molar amount of molar oxygen contained, has an increased molar
  • the propene is largely converted into acrolein as it passes through the reaction zones and is separated as such from the product gas mixture leaving the last reaction zone as the target product and not recycled as cycle gas, which is why the advantage of the procedure according to the invention is primarily that Reduced amount of inert gas to be circulated. at
  • the advantage of the process according to the invention outlined above is, of course, the more pronounced the greater the number of reaction zones used into which molecular oxygen or a gas containing molecular oxygen is metered, ie the lower the proportion of molecular oxygen in the reaction gas mixture chosen within a reaction zone becomes.
  • the number of reaction zones into which molecular oxygen or a gas containing molecular oxygen is metered in is generally not more than three in the process according to the invention; the process according to the invention, including the first reaction zone, preferably comprises two reaction zones.
  • the process according to the invention, including the first reaction zone preferably comprises two reaction zones.
  • no further reaction zone in both no molecular oxygen and no molecular oxygen corresponds' supporting gas is added - with the advantage fiction, includes. If the molecular oxygen is metered in as a constituent of a gas mixture, for example in the form of air, the other constituents of the gas mixture normally form inert gases with respect to the process according to the invention.
  • inert or dilution gases for the process according to the invention. These are, for example, N 2 , CO, C0, H 2 0, saturated hydrocarbons (in particular Ci to C 5 alkanes) and / or noble gases.
  • the different reaction zones can be charged with one and the same but also with different catalysts. It is only essential according to the invention that the catalyst feed ensures sufficient selectivity of acrolein formation. This is the case with numerous prior art catalysts. Such catalysts are e.g. those of DE-A 2 909 592, especially those from Example 1 of said document. Alternatively, however, the multimetal oxide catalysts II or II 'of DE-A 19 753 817 can also be used. This applies in particular to the exemplary embodiments listed in these documents. Especially when they are designed as hollow cylinder full catalysts as described in EP-A 575 897.
  • the ACF-2 multimetal oxide catalyst from Nippon Shokubai which contains Bi, Mo and Fe, can of course also be used.
  • the catalyst feed to a single reaction zone can consist of a single catalyst, a mixture of catalysts or a sequential arrangement of different catalysts.
  • the reaction temperature in the reaction zones of the process according to the invention is expediently chosen to be from 300 ° C. to 450 ° C., preferably from 320 to 390 ° C.
  • reaction temperature can be made uniform or different in all reaction zones. As a rule, it is advantageous if the reaction temperatures in Direction of increasing propene conversion within the reaction zone increases.
  • the at least two reaction zones required according to the invention can be designed as a fluidized bed and / or as a fixed bed. Furthermore, according to the invention, they can be implemented in a single reactor or else in separate reactors connected in series.
  • the process according to the invention is preferably carried out in multi-contact tube fixed bed reactors.
  • the two-zone multi-contact tube fixed-bed reactor described in US Pat. No. 4,203,906 is suitable, for example, for carrying out the process according to the invention in a single rector if, when the reaction gas passes into the second reaction zone, the possibility of metering in molecular oxygen or a molecular oxygen-containing one Gases is created.
  • the reaction gas mixture and the heat exchange medium viewed in the individual reaction zone, can be conducted in cocurrent and / or in countercurrent.
  • the flow of the heat exchange medium can be designed as a pure longitudinal flow, as a longitudinal flow with a superimposed transverse flow or as a radial flow, as described in DE-A 2 201 528.
  • a single reaction zone will be designed as a separate multi-contact tube fixed bed reactor within the process according to the invention.
  • the latter can be designed and operated, for example, like those described in EP-A 700 714.
  • the reaction gas starting mixture fed to the first reaction zone can contain a propene: oxygen: essentially indifferent gases volume (NL) ratio of (> 1.0 to 3.0): 1: (10 to 1.5), preferably of (1, 1 to 2.0): 1: (10 to 1.5), particularly preferably from (1.2 to 1.5): 1: (10 to 1.5).
  • NL indifferent gases volume
  • the reaction pressure is usually 0.5 to 5 bar, preferably 1 to 3 bar.
  • the total space load is frequently 1500 to 2500 Nl / l / h.
  • the molar ratio of propene: molecular oxygen in the reaction gas starting mixture fed to the first reaction zone is inevitably> 1 (as a rule it will be ⁇ 3)
  • the molar ratio of (propene and acrolein): molecular oxygen in the reaction gas mixture of each reaction zone is> 1.
  • the molar ratio of propene: oxygen in the reaction gas starting mixture can be, for example (> 1.0 to 3.0): 1, often (1.1 to 2.0) : 1 and in the reaction gas mixture fed to the second multi-contact tube fixed bed reactor after the addition of molecular oxygen, for example 1: (> 1.0 to 3.0), often 1: (1.5 to 2.0).
  • the propene conversion in the first multi-contact tube fixed bed reactor will advantageously be 20 to 60 mol%, often 40 to 60 mol%, based on the propene supplied. The above applies in general in the case of a two-zone implementation.
  • recycle gas routing can normally be completely dispensed with or restricted to recycling unreacted propene.
  • acrolein in the context of the process according to the invention, no pure acrolein is obtained, but a gas mixture from which the acrolein can be separated in a manner known per se (e.g. by absorption in an aqueous medium with subsequent rectificative separation).
  • the acrolein so separated can be used as an intermediate for the synthesis of various end products.
  • it can also be used in a heterogeneously catalyzed gas-phase partial oxidation of acrolein with molecular oxygen on catalysts in the solid state to produce acrylic acid.
  • the reaction gases containing the acrolein of the last propenoxidation zone are normally transferred to this at least one further oxidation zone without removal of secondary components. If necessary, they undergo intermediate cooling beforehand.
  • this further heterogeneously catalyzed gas-phase partial oxidation of acrolein to acrylic acid can be carried out in several reaction zones connected in series, in a completely analogous manner to the propene partial oxidation according to the invention. However, it can also be carried out in a manner known per se in a single reaction zone or in a plurality of reaction zones connected in parallel with one another.
  • the reaction zones are also advantageously implemented as separate multi-contact tube fixed-bed reactors, as is e.g. is described in EP-A 700 893 and the prior art cited therein or in DE-A 4 431 949, DE-A 4 442 346, DE-A 19 736 105 or EP-A 731 082.
  • Multi-metal oxides suitable as catalysts in this regard are e.g. those that contain the elements Mo and V.
  • the reaction temperature in the reaction zones is expediently chosen to be 200 to 300 ° C., preferably 220 to 290 ° C.
  • the reaction pressure in the reaction zones is usually 0.5 to 5 bar, preferably 1 to 3 bar.
  • the total space load of the multi-contact tube fixed bed reactors is usually 1000 to 2500 Nl / l / h.
  • Suitable catalysts for the acrolein partial oxidation to acrylic acid are, for example, those of the general formula I or I 'from DE-A 4 442 346.
  • the multimetal oxide catalysts of DE-A 19736105 in particular the exemplary embodiments mentioned in the abovementioned document, can also be used.
  • the ACS-4 multimetal oxide catalyst from Nippon Shokubai, which includes Bi, Mo and Fe, can of course also be used in the acrolein oxidation stage.
  • the statements regarding the propene partial oxidation according to the invention apply in a corresponding manner.
  • additional molecular oxygen to the product gas mixture containing acrolein from the last propene oxidation zone before it is introduced into the at least one acrolein oxidation zone.
  • This can be in the form of air, in the form of nitrogen-depleted air or in the form of pure oxygen.
  • additional dilution gases known essentially as indifferent, can be added at this point as desired.
  • the gas mixture leaving the last acrolein oxidation zone naturally does not consist of pure acrylic acid, but of a gas mixture containing the latter, from which acrylic acid can be separated in a manner known per se.
  • the various known variants of acrylic acid separation are summarized, for example, in DE-A 19 600 955.
  • the acrolein could also be separated from the reaction gas mixture leaving the last propene oxidation zone.
  • a common feature of the separation process is that the desired product is separated from the product gas mixture either by absorption with a solvent (cf. also DE-4308087) or by absorption with water and / or by partial condensation.
  • the resulting absorbate or condensate is then worked up by distillation (optionally with the addition of an azeotropic entrainer) and / or crystallization ', and essentially pure acrylic acid or pure acrolein is thus obtained.
  • the dividing line is drawn in all cases so that a residual gas stream essentially free of acrylic acid and / or acrolein is formed, the main component of which is the indifferent diluent gases and the partial or can be completely reused as inert diluent via recycle gas.
  • the advantage of the process according to the invention is that it minimizes the amount of circulating gas in the inert diluent gas used. It is of particular importance according to the invention that this is possible without reducing the space-time yield.
  • the process according to the invention also makes use of the fact that H 2 0 is formed as a by-product of the relevant catalytic gas phase oxidation and acts as an additional inert diluent gas along the reaction path.
  • a first reaction tube (V2A steel; length 3.80 m; 2.0 mm wall thickness; 2.6 cm inner diameter) is charged with the aforementioned reaction gas starting mixture as the first propene oxidation zone Temperature of 340 ° C is salt bath cooled. In the direction of flow, the reaction tube is loaded with a pre-fill of steatite balls (diameter: 4-5 mm) over a length of 50 cm.
  • a bed of the 5 multimetal oxide catalyst according to Example 1, 3. / Multimetal Oxide II from DE-A 19753817 follows on a contact tube length of 3.00 m.
  • the product gas mixture leaving the first reaction tube in an amount of 66.5 mol / h is indirectly cooled directly to 200 ° C. to avoid undesired afterburning and has the following composition 10:
  • a second reaction tube (V2A steel, length 3.80 m; 2.0 mm wall thickness; 2.6 cm inner diameter) is charged as the second propene oxidation zone at an inlet pressure of 1.75 bar and an inlet temperature of 200 ° C is cooled along its entire length to a temperature of 350 ° C salt bath.
  • V2A steel V2A steel, length 3.80 m; 2.0 mm wall thickness; 2.6 cm inner diameter
  • These reaction tubes (V2A steel; length: 3.80 m, 2.0 mm wall thickness; 2.6 cm inner diameter) are each initially in the flow direction over a length of 50 cm with a bed of steatite balls (diameter: 4-5 mm ) loaded.
  • a bed of the multimetal oxide catalyst according to Example b, Sl of DE-A 4442346 follows on a contact tube length of 2.70 m.
  • the entire length of the reaction tubes is kept at 270 ° C. with a salt bath.
  • the outlet pressure of the reaction tubes is 1.35 bar.
  • the product gas mixture leaving the two parallel reaction tubes is combined to form 137.6 mol / h of a total product gas mixture of the following composition:
  • the leaving the acrolein oxidation hot total product - is the gas mixture in a venturi scrubber (quench apparatus) by di ⁇ rect contact with the region of the narrowest cross-section of the Venturi tube mounted slots owneddüsende quench liquid (140-150 ° C) from 57.4 wt -.% Diphenyl ether, 20.7% by weight diphenyl and 20% by weight o-dimethyl phthalate cooled to a temperature of approx. 160 ° C.
  • the drop-like liquid portion of the quench liquid is separated from the gas phase consisting of reaction gas and vaporized quench liquid in a downstream droplet separator (supply container with gas pipe carried away at the top) and recycled in a circuit I to the venturi scrubber.
  • a partial stream of the recycled quench liquid is subjected to a solvent distillation, the quench liquid being distilled over and high-boiling secondary components which are burned up remaining.
  • the over-distilled quench liquid is fed to the outlet of the absorption column described below.
  • the gas phase which has a temperature of approx. 160 ° C., is fed into the lower part of a packed column (3 m high; double jacket made of glass; inner diameter 50 mm; packed zones of lengths (from bottom to top) 90 cm, 90 cm and 50 cm; the packing zones are thermostatted from bottom to top as follows: 90 ° C, 60 ° C, 20 ° C; the penultimate and the last packing zone are separated by a chimney tray; the packing bodies are stainless steel metal coils with a coil diameter of 5 mm and a helix length of 5 mm; the absorbent is fed in directly above the middle packing zone) and the counterflow of 4900 g / h which also consists of 57.4% by weight diphenyl ether, 20.7% by weight diphenyl and 20% by weight o-Dimethylphthalat composite, applied at a temperature of 50 ° C exposed absorbent.
  • acrolein and acetic acid absorbed the discharge of the absorption column, which in addition to acrylic acid and low-boiling by-products, is heated in a heat exchanger indirectly to 100 ° C and at the head of a desorption column given that run also as a packed column, a ⁇ length of 2 m is (double jacket made of glass; 50 mm inner diameter; filler: stainless steel helixes with a helix diameter of 5 mm and a helix length of 5 mm; a filler zone length 1 m; thermostatted to 120 ° C).
  • the low boiling point compared to acrylic acid is the components such as acrolein and acetic acid are largely removed from the acrylic acid / absorbent mixture by stripping with residual gas leaving the absorption column (22.8 mol / h residual gas; countercurrent; feed temperature 120 ° C.).
  • the loaded stripping gas leaving the desorption column is recirculated and combined with the hot reaction gas of the acrolein oxidation stage before it enters the venturi quench.
  • the non-absorbed gas mixture leaving the second packed zone upwards in the absorption column is further cooled in the third packed zone in order to remove the easily condensable part of the secondary components contained therein, e.g. Separate water and acetic acid by condensation.
  • This condensate is called acid water.
  • part of the acid water above the third packing zone of the absorption column is returned to the absorption column at a temperature of 20 ° C.
  • the acid water is extracted below the uppermost packing zone from the chimney floor attached there.
  • the reflux ratio is 200.
  • the amount of acid water to be taken off continuously is 15.6 mol / h. In addition to 90.3% by weight of water, it also contains 2.60% by weight of acrylic acid. If necessary, this can be recovered as described in DE-A 19600955.
  • the residual gas ultimately leaving the absorption column is partly used for stripping and otherwise forms exhaust gas.
  • the bottom liquid of the desorption column is fed from the bottom to a bottom column containing 57 dual flow trays on the 8th tray (inside diameter: 50 mm; length: 3.8 m; top pressure: 100 mbar; bottom pressure: 280 mbar; bottom temperature: 195 ° C; on the 9th floor there is a pressure loss resistor;) and rectified in the same.
  • a gas stream enriched with low boilers and containing acrylic acid is drawn off at the top of the rectification column and, after its complete condensation, is recirculated to the absorption column in a cooling case (32 g / h) above the lowest packing zone.
  • the absorbent free of low boilers and almost free of acrylic acid is withdrawn from the bottom of the rectification column and recycled into the absorption column above the second packing zone (viewed from below).
  • the reflux at the head of the rectification column is' phenothiazine was added as a polymerization inhibitor and in such amounts that the side draw containing 300 ppm of phenothiazine (a schematic representation of the work-up procedure of the reaction gas of the acrolein oxidation stage is shown in DE-A 19600955; moreover, the working-up procedure is also - DE-A 4308087 shown).
  • the composition of the residual gas leaving the absorption column is
  • the amount of the residual gas stream is 110.3 mol / h.
  • Circulating gas flow can be completely omitted.
  • reaction gas mixture is divided into two equal-sized partial flows, which are used to feed two reaction tubes (V2A steel; length 3.80 m; 2.0 mm wall thickness; 2.6 cm inside diameter) connected in parallel as propenoxidation zones.
  • reaction tubes like the propenoxidation tubes in Example A), are each filled with a pre-fill of steatite spheres (diameter: 4-5 mm) over a length of 50 cm.
  • a bed of the multimetal oxide catalyst according to Example 1, 3rd / multimetal oxide II from DE-A 19753817 follows on a contact tube length of 3.00 m.
  • the length of both reaction tubes is salt bath cooled to a temperature of 350 ° C.
  • the product gas streams leaving the reaction tubes are combined to a total product gas stream of 262.1 mol / h of the following composition:
  • reaction gas mixture is divided into two partial streams of equal size, which are fed with an inlet pressure of 1.55 bar and an inlet temperature of 200 ° C to feed two reaction tubes connected in parallel as acrolein oxidation zones (V2A steel; length: 3.80 m; 2, 0 mm wall thickness; 2.6 cm inner diameter) can be used.
  • acrolein oxidation zones V2A steel; length: 3.80 m; 2, 0 mm wall thickness; 2.6 cm inner diameter
  • These reaction tubes like the acrolein oxidation tubes in Example A), are each supplied with a pre-fill of steatite balls (diameter: 4-5 mm) over a length of 50 cm.
  • a bed of the multimetal oxide catalyst according to Example b, S1 of DE-A 4442346 follows on a contact tube length of 3.00 m.
  • the length of both reaction tubes is salt bath cooled to a temperature of 270 ° C.
  • the product gas streams leaving the reaction tubes are indirectly cooled directly to 200 ° C. in order to avoid undesired afterburning and combined to a total product gas stream of 275.4 mol / h of the following composition:
  • the space-time yield of crude acrylic acid in the classic parallel connection corresponds to that in Example A) according to the invention.
  • the classic parallel connection requires the recirculation of 140.5 mol / h of recycle gas in order to operate the gas phase partial oxidation safely outside the explosion area from the start.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de fabrication d'acroléine par oxydation partielle en phase gazeuse catalytique hétérogène, caractérisé en ce qu'on fait réagir un mélange gazeux réactionnel de départ, renfermant du propène et de l'oxygène moléculaire, dans un rapport molaire C>3<H>6<: O>2< > 1, dans des zones de réaction successives, à température élevée, sur des catalyseurs à l'état physique solide, et en ce qu'une quantité supplémentaire d'oxygène moléculaire est ajoutée, au cours de l'oxydation partielle, au mélange gazeux réactionnel.
EP00912429A 1999-01-22 2000-01-15 Procede de fabrication d'acroleine par oxydation partielle en phase gazeuse catalytique heterogene du propene Withdrawn EP1144352A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19902562 1999-01-22
DE19902562A DE19902562A1 (de) 1999-01-22 1999-01-22 Verfahren zur Herstellung von Acrolein durch heterogen katalysierte Gasphasen-Partialoxidation von Propen
PCT/EP2000/000304 WO2000043341A2 (fr) 1999-01-22 2000-01-15 Procede de fabrication d'acroleine par oxydation partielle en phase gazeuse catalytique heterogene du propene

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EP1144352A2 true EP1144352A2 (fr) 2001-10-17

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EP00912429A Withdrawn EP1144352A2 (fr) 1999-01-22 2000-01-15 Procede de fabrication d'acroleine par oxydation partielle en phase gazeuse catalytique heterogene du propene

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US (1) US6410785B1 (fr)
EP (1) EP1144352A2 (fr)
CN (1) CN1336908A (fr)
BR (1) BR0007601A (fr)
DE (1) DE19902562A1 (fr)
WO (1) WO2000043341A2 (fr)

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US7115776B2 (en) 2002-07-18 2006-10-03 Basf Aktiengesellschaft Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound
US6958414B2 (en) 2002-12-16 2005-10-25 Basf Aktiengesellschaft Preparation of at least one organic compound by heterogeneously catalyzed partial gas-phase oxidation
JP4041420B2 (ja) * 2003-03-14 2008-01-30 株式会社日本触媒 気相反応装置の緊急停止方法
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